Separator for Electricity Storage Devices, and Electricity Storage Device

ABSTRACT

A separator for electricity storage devices, which comprises a porous layer that contains a polyolefin resin and an ionic compound, and which is configured such that: the content of the ionic compound in the porous layer is from 5% by mass to 99% by mass (inclusive); and the degree of whiteness of this separator is more than 98.0.

FIELD

The present invention relates to a separator for electricity storagedevices and an electricity storage device using the separator.

BACKGROUND

Electricity storage devices have been used in a wide range ofapplications such as a power source for consumer appliances, automotiveonboard power source, stationary power source, etc. Among theseelectricity storage devices, a lithium ion secondary battery hasexcellent features such as high energy density and high durability, andthus its use as a power source for electric vehicles has been rapidlyexpanding in recent years.

In the lithium ion secondary battery, a polyolefin microporous membraneis generally used as a separator. The separator is disposed between apositive electrode and a negative electrode to prevent electronconduction due to direct contact or short circuit between the positiveand negative electrodes, while allowing ion conduction through anelectrolytic solution held in microporous pores of the separator.

An electricity storage device for electric vehicles needs to haveadvanced input/output characteristics since charge and discharge with alarge current in a short time such as quick charge and a regenerativebrake are frequently carried out. Furthermore, since the electricitystorage device is often disposed at high density in a limited space of avehicle, the temperature of the battery tends to rise, and a high levelof heat resistance of the separator is required from the viewpoint ofensuring safety.

In recent years, various attempts have been considered for improvementon heat resistance of separators. The most widely used method is amethod for forming a heat-resistant layer mainly containing an inorganicfiller and/or a heat-resistant organic resin on a base film using apolyolefin microporous membrane. For example, Patent Document 1describes the heat-resistant layer mainly containing silica, that isformed on a polyethylene microporous membrane to improve heat resistanceof the separator.

On the other hand, there has been proposed a method for enhancing heatresistance of a separator. For example, Patent Document 2 discloses analumina-containing polyethylene microporous membrane fabricated bycombined use of a polyethylene resin and alumina. Patent Document 2specifically describes that the microporous membrane composed of highdensity polyethylene and alumina particles (average particle size of 2nm) enables to maintain the insulating property by the alumina particleseven at elevated temperatures.

Moreover, in Patent Documents 3 and 4, there is also proposed a methodfor fabricating a silica-containing polyethylene microporous membraneusing a polyethylene resin and silica in combination. Patent Documents 3and 4 specifically describe that the shrinkage of the microporousmembrane can be suppressed even at elevated temperatures exceeding themelting point of polyethylene by filling the polyethylene resin withsilica in the condensed concentration.

Further, Patent Document 5 discloses a method for fabricating a bariumsulfate-containing polyolefin microporous membrane by mixing apolyolefin resin and barium sulfate. Specifically, polyolefin resinssuch as high density polyethylene, soft polypropylene, etc., and bariumsulfate (average particle size of 660 nm) as a filler are mixed, and theobtained mixture is stretched to strip at an interface between the resinand the filler, forming a porous membrane.

PRIOR ART DOCUMENTS Patent Documents

-   [Patent Document 1] WO2012/005139-   [Patent Document 2] Japanese Unexamined Patent Publication (Kokai)    No. 1998(H10)-50287-   [Patent Document 3] WO2010/108148-   [Patent Document 4] Japanese Unexamined Patent Publication (Kokai)    No. 2010-262785-   [Patent Document 5] Japanese Unexamined Patent Publication (Kokai)    No. 2005-71979

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

However, since in the technology described in Patent Document 1 wherebythe polyethylene microporous membrane is used as a base material of theheat-resistant layer, polyethylene melts and flows at an elevatedtemperature, and the insulation of the separator may not be held.Moreover, this technology requires a process for manufacturing the basematerial and a process for forming the heat-resistant layer, also givingrise to problems of multiple processes and low productivity.

Further, in the technology described in Patent Documents 2 to 4 wherebythe polyolefin microporous membrane contains metal oxide fillers, it isnecessary to knead the polyolefin and the metal oxide at an elevatedtemperature. When the polyolefin comes into contact with the metal oxideat elevated temperatures, the polyolefin incurs metal oxide-induceddeterioration, and the separator may turn to yellow. There is a concernabout a voltage resistance property and oxidation resistance of thedeteriorated polyolefin, which is not preferable from the viewpoint ofenhancing reliability and safety of an electricity storage device.Moreover, in the electricity storage device held at elevatedtemperatures, the metal oxide may occasionally react with anelectrolytic solution, which is also unpreferable from the viewpoint ofworsening battery characteristics such as cycle characteristics, etc.,or impairing safety due to battery swelling by gas generation.

Patent Document 5 describes a technology whereby the membrane isrendered porous by interfacial stripping of the polyolefin resin and thefiller. If the particle size of the filler is large, there is alikelihood that a void with a large pore size is generated by accident,and when the membrane is used as a separator of electric storagedevices, a micro short circuit or self-discharge may occur. Moreover,fillers with large particle sizes are often manufactured by pulverizingnatural quarry minerals and therefore contain impurities such as metaloxides and halogen elements, which accelerates the deterioration of thepolyolefin and may turn the separator to yellow.

An object of the present invention, in light of the above situations, isto provide a separator for electricity storage devices characteristic ofhaving excellent heat resistance and ion permeability without impairingthe durability of the electricity storage device, and with lessdeterioration of polyolefin, and to provide an electricity storagedevice comprising the separator.

Means for Solving the Problem

The present inventors have conducted much diligent experimentation withthe aim of solving the problems described above. As a result, thepresent inventors have found that the problem can be solved by aseparator for electricity storage devices which has a porous layercomprising a polyolefin resin and an ionic compound as well as aspecific degree of whiteness, and thus have completed the presentinvention.

Namely, the present invention is as described below.

[1] A separator for electricity storage devices, which has a porouslayer comprising a polyolefin resin and an ionic compound, wherein acontent of the ionic compound in the porous layer is 5% by weight ormore and 99% by weight or less in the porous layer and a degree ofwhiteness of the separator is greater than 98.0.[2] The separator for electricity storage devices according to [1],wherein the degree of whiteness is 98.5 or more and 105 or less.[3] The separator for electricity storage devices according to [1] or[2], wherein the content of the ionic compound in the porous layer is 5%by weight or more and less than 50% by weight.[4] The separator for electricity storage devices according to [1] or[2], wherein the content of the ionic compound in the porous layer is86% by weight or more and 99% by weight or less.[5] The separator for electricity storage devices according to any oneof [1] to [4], wherein the polyolefin resin contains polyethylene havinga viscosity-average molecular weight of 600,000 or more and 5,000,000 orless.[6] The separator for electricity storage devices according to any oneof [1] to [5], wherein a content of metal oxide in the separator forelectricity storage devices is 10% by weight or less.[7] The separator for electricity storage devices according to any oneof [1] to [6], wherein the ionic compound has one or more anionsselected from the group consisting of a sulfate ion, a nitrate ion, aphosphate ion, and a halide ion.[8] The separator for electricity storage devices according to any oneof [1] to [7], wherein the ionic compound has one or more cationsselected from the group consisting of an alkali metal ion and analkaline earth metal ion.[9] The separator for electricity storage devices according to any oneof [1] to [8], wherein the ionic compound is barium sulfate.[10] The separator for electricity storage devices according to any oneof [1] to [9], wherein an average particle size of the ionic compound is5 nm or more and 600 nm or less.[11] The separator for electricity storage devices according to any oneof [1] to [10], wherein an average pore size of the separator forelectricity storage devices is 10 nm or more and 100 nm or less.[12] The separator for electricity storage devices according to any oneof [1] to [11], wherein an air permeability of the separator forelectricity storage devices is 10 seconds/100 ml or longer and 500seconds/100 ml or shorter.[13] The separator for electricity storage devices according to any oneof [1] to [12], wherein a puncture strength of the separator forelectricity storage devices is 100 gf or more and 600 gf or less.[14] The separator for electricity storage devices according to any oneof [1] to [13], wherein a viscosity-average molecular weight of thepolyolefin resin comprised in the separator for electricity storagedevices is 300,000 or more and 5,000,000 or less.[15] An electricity storage device comprising a positive electrode, anegative electrode, and the separator for electricity storage devicesaccording to any one of [1] to [14].

Effects of the Invention

The present invention enables to provide a separator for electricitystorage devices having excellent heat resistance and ion permeabilitywithout impairing durability of an electricity storage device, and withless deterioration of polyolefin, and to provide an electricity storagedevice comprising the separator.

MODE FOR CARRYING OUT THE INVENTION

Embodiments for carrying out the invention (hereunder referred to as“the present embodiment”) will now be explained in detail. It is to beunderstood, however, that the present invention is not limited to thefollowing embodiments and may be implemented with appropriatemodifications within the scope of its gist.

<<Porous Layer>>

The separator for electricity storage devices according to the presentembodiment has a porous layer comprising a polyolefin resin and an ioniccompound. The porous layer contributes to improve not only heatresistance and ion permeability of the separator but also safety andinput/output characteristics of an electricity storage device withoutdeterioration of the electricity storage device by combined use of thepolyolefin resin and the ionic compound.

The thickness of the porous layer is preferably 1 μm or more, morepreferably 2 μm or more, and still more preferably 3 μm or more. Whenthe thickness of the porous layer is 1 μm or more, the heat resistanceof the separator is improved. Also, the thickness of the porous layer ispreferably 20 μm or less, more preferably 18 μm or less, and still morepreferably 16 μm or less. When the thickness of the porous layer is 20μm or less, the energy density of an electricity storage device can beincreased.

The porosity of the porous layer is preferably 30% or more, morepreferably 35% or more, and still more preferably 40% or more from theviewpoint of enhancing the ion permeability of the separator. On theother hand, from the viewpoint of maintaining the structural stabilityof the separator, it is preferably 70% or less, more preferably 65% orless, and still more preferably 60% or less.

The thickness proportion of the porous layer relative to the wholeseparator for electricity storage devices is preferably greater than 0%and 100% or less, more preferably 10% or more and 100% or less, andstill more preferably 20% or more and 100% or less in consideration ofthe heat resistance, ion permeability and physical strength of theseparator. The thickness proportion of the porous layer being 100% ispreferred to facilitate manufacturing. On the other hand, even if thethickness proportion of the porous layer is less than 100%, since thehigh heat resistance of the porous layer can be imparted to the wholeseparator, it may be less than 100%.

The method for fabricating the porous layer is not particularly limited,and multiple methods can be employed. Specifically, stretching stepssuch as uniaxial stretching, biaxial stretching, etc.; removal steps ofa third component other than the polyolefin resin and ionic compound bythe means such as extraction, volatilization, decomposition, etc., maybe applied. As the third component, plasticizers such as liquidparaffin, dioctyl phthalate, etc.; solvents such as acetone, water,etc.; and inorganic substances such as calcium carbonate, silica, etc.,can be used alone or in combination thereof. As a method for fabricatingthe porous layer, from the viewpoint of reducing a manufacturing cost ofthe separator and improving quality such as thickness uniformity, etc.,it is preferable to have at least the stretching step, and morepreferable to have the stretching step and the third component removalstep, still more preferable to have the stretching step and the thirdcomponent extraction step, and particularly preferable to have thebiaxial stretching step and the plasticizer extraction step. When theporous layer is fabricated by these methods, not only the porous layercan be formed uniformly but also physical property adjustment such asthe entire thickness, porosity, etc., of the separator for electricitystorage devices is facilitated.

<<Polyolefin resin>>

The separator for electricity storage devices according to the presentembodiment has a porous layer comprising a polyolefin resin. Thepolyolefin resin used in the present embodiment is a polyolefin resinused for general extrusion, injection, inflation, blow molding, etc.,and is a polymer comprising olefin hydrocarbon as a monomer component,such as a homopolymer, copolymer and multistage polymer of ethylene,propylene, 1-butene, 2-butene, 4-methyl-1-pentene, 1-hexene, 1-octene,etc. Also, the polyolefin selected from the group consisting of thehomopolymer, copolymer, and multistage polymer can be used alone or inadmixture.

As the polyolefin resin, examples thereof include low densitypolyethylene (density 0.910 g/cm³ or more and less than 0.930 g/cm³),linear low density polyethylene (density 0.910 g/cm³ or more and 0.940g/cm³ or less), middle density polyethylene (density 0.930 g/cm³ or moreand less than 0.942 g/cm³), high density polyethylene (density 0.942g/cm³ or more), ultra-high molecular weight polyethylene (density 0.910g/cm³ or more and 0.970 g/cm³ or less), isotactic polypropylene,syndiotactic polypropylene, atactic polypropylene, polybutene,polymethylpentene and ethylene propylene rubber.

The proportion of the polyolefin resin in the porous layer is preferablygreater than 0% by weight, more preferably 1% by weight or more, andstill more preferably 2% by weight or more. When the proportion of thepolyolefin resin is greater than 0% by weight, not only formation of theporous layer is facilitated, but also physical strength can be impartedto the porous layer. Moreover, this proportion is preferably 95% byweight or less, more preferably 90% by weight or less, and still morepreferably 85% by weight or less. When the proportion of the polyolefinresin is 95% by weight or less, the heat resistance of the porous layertends to be high.

The proportion of the polyolefin resin in the entire separator forelectricity storage devices is preferably 5% by weight or more, morepreferably 10% by weight or more, and still more preferably 15% byweight or more. When the proportion of the polyolefin resin is 5% byweight or more, sufficient physical strength can be imparted to theseparator. Moreover, this proportion is preferably 95% by weight orless, more preferably 90% by weight or less, and still more preferably85% by weight or less. When the proportion of the polyolefin resin is95% by weight or less, the heat resistance of the separator tends to behigh.

The polyolefin resin preferably contains high density polyethylene. Theproportion of the high density polyethylene in the polyolefin resin ispreferably 10% by weight or more, more preferably 35% by weight or more,still more preferably 50% by weight or more, and may be 100% by weight.When the proportion of the high density polyethylene in the polyolefinresin is 10% by weight or more, the strength of the separator isincreased due to the entanglement of the high density polyethylenemolecular chains.

The polyolefin resin preferably contains high molecular weightpolyethylene. The proportion of the high molecular weight polyethylenein the polyolefin resin is preferably 30% by weight or more, morepreferably 50% by weight or more, and still more preferably 65% byweight or more, and it may be 100% by weight. The viscosity-averagemolecular weight (Mv) of the high molecular weight polyethylene ispreferably 600,000 or higher and 5,000,000 or lower, more preferably650,000 or higher and 4,000,000 or lower, and still more preferably700,000 or higher and 3,000,000 or lower. The viscosity-averagemolecular weight can be determined by measuring the intrinsic viscosityat 135° C. in a decalin solvent based on ASTM-D4020 and calculating fromthe equation corresponding to the polyolefin resin.

For polyethylene, My can be calculated by the following equation.

[η]=6.77×10⁻⁴ Mv^(0.67)

For polypropylene, My can be calculated by the following equation.

[η]=1.10×10⁻⁴ Mv^(0.80)

It is preferable to use the polyolefin resin having a viscosity-averagemolecular weight of 600,000 or more from the viewpoint of maintaining ahigh melt tension to ensure favorable moldability when melt-kneading apolyolefin resin composition, and from the viewpoint of impartingsufficient entanglement to the polyolefin resin molecules to increasestrength of the separator. On the other hand, adjusting theviscosity-average molecular weight to 5,000,000 or less is preferablefrom the viewpoint of improving stability of extrusion molding of thepolyolefin resin.

From the viewpoint of improving the heat resistance of the separator,the polyolefin resin preferably contains polypropylene. The proportionof polypropylene in the polyolefin resin is preferably 1% by weight ormore, more preferably 5% by weight or more, and still more preferably15% by weight or more. Also, the proportion of polypropylene in thepolyolefin resin is preferably 30% by weight or less, more preferably20% by weight or less, and still more preferably 10% by weight or less.It is preferable to adjust the proportion of polypropylene to 1% byweight or more from the viewpoint of improving the heat resistance ofthe separator. On the other hand, from the viewpoint of enhancing theuniformity of the separator, the proportion of polypropylene ispreferably 30% by weight or less.

In the polyolefin resin used in the present embodiment, if necessary,antioxidants such as phenol-based, phosphorus-based, sulfur-basedantioxidants, etc., metal soaps such as calcium stearate, lithiumstearate, etc., additives such as ultraviolet light absorbers, lightstabilizers, antistatic agents, antifogging agents, color pigments,etc., can be mixed and used, provided that the advantages of the presentinvention are not impaired.

<<Ionic compound>>

The separator for electricity storage devices according to the presentembodiment has a porous layer comprising an ionic compound. The ioniccompound used in the present embodiment refers to a compound that iscomposed of a combination of one or more cations and one or more anionsand is electrically neutral based on strong chemical bonding such asionic bonding.

The ionic compound is not particularly restricted provided it iscomposed of a combination of a cation and an anion, however, examplesthereof include sulfates such as lithium sulfate, sodium sulfate,magnesium sulfate, calcium sulfate, barium sulfate, aluminum sulfate,etc.; nitrates such as lithium nitrate, sodium nitrate, magnesiumnitrate, potassium nitrate, etc.; phosphates such as lithium phosphate,sodium phosphate, magnesium phosphate, potassium phosphate, etc.;halides such as lithium fluoride, sodium chloride, sodium bromide, etc.;

carbonates such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate, etc.;

hexafluorophosphates such as lithium hexafluorophosphate, etc.;tetrafluoroborates such as lithium tetrafluoroborate, etc.; andperchlorates such as lithium perchlorate, etc.

The anion of the ionic compound is preferably at least one speciesselected from the group consisting of a sulfate ion, nitrate ion,phosphate ion, and halide ion in consideration of both the stabilityinside an electricity storage device and the cost. It is more preferablyat least one species selected from the group consisting of a sulfateion, phosphate ion, and halide ion, furthermore preferably a sulfate ionand/or phosphate ion, and particularly preferably a sulfate ion.

Moreover, when considering both the stability inside the electricitystorage device and the cost, the cation of the ionic compound ispreferably at least one species selected from the group of an alkalimetal ion and alkaline earth metal ion, more preferably a lithium ion,sodium ion, potassium ion, magnesium ion, calcium ion, strontium ion, orbarium ion, still more preferably a magnesium ion, calcium ion, orbarium ion, and particularly preferably a barium ion. Namely, as theionic compound, barium sulfate is most preferred in consideration of thestability inside the electricity storage device.

Moreover, the ionic compound may be used singly, and two or more thereofmay be used in combination.

The shape of the ionic compound may be, for example, plate-like, scaly,acicula, columnar, spherical, polyhedral, massive, etc., and s pluralityof ionic compounds having the above shapes may be used in combination.The shape of the ionic compound is not particularly limited, howeverfrom the viewpoint of improvement of heat resistance, columnar,spherical or polyhedral ions are preferred, and spherical ions are morepreferred.

Carbonates such as calcium carbonate, etc., have long been widely usedas fillers for various polymers, and their performance as fillers hasbeen demonstrated in various applications. However, carbonate used in aspecial environment such as the inside of an electricity storage deviceis not preferred because the carbonate may be decomposed to generatecarbon dioxide. Other than carbonates, ionic compounds such as sulfates,phosphates, and halides are preferable since these have high stabilityinside the electricity storage device.

Metal oxides such as alumina, etc., are known to be more covalent thanionic as the nature of the chemical bonds of the metal oxide. Therefore,in the present invention, alumina, boehmite, silica, titania, yttria,zirconia, lithium oxide, sodium oxide, potassium oxide, magnesium oxide,calcium oxide, vanadium oxide, chromium oxide, manganese oxide, ironoxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide and ceriumoxide are classified as metal oxides and not included in ioniccompounds. Also, compounds composed of a plurality of metal oxides suchas potassium titanate (K₂O.8TiO₂), etc., are also classified as metaloxides.

The content of the metal oxide in the separator for electricity storagedevices is preferably 10% by weight or less, more preferably 8% byweight or less, still more preferably 6% by weight or less, andparticularly preferably 4% by weight or less. Due to this, the promotionof deterioration of the polyolefin tends to be suppressed.

The proportion of the ionic compound in the porous layer (i.e., thecontent of the ionic compound in the porous layer) is preferably 5% byweight or more, more preferably 10% by weight or more, and still morepreferably 15% by weight or more. When the proportion of the ioniccompound is 5% by weight or more, the heat resistance of the porouslayer tends to be improved, however from the viewpoint of securingsufficient heat resistance in actual use, it is desirably 86% by weightor more, more desirably 90% by weight or more, and still more desirably95% by weight or more. On the other hand, from the viewpoint ofenhancing the ion permeability of the porous layer while maintaining thephysical strength thereof, it is preferably 5% by weight or more,preferably 10% by weight or more, and still more preferably 15% byweight or more.

Also, this proportion is 99% by weight or less, more preferably 98.5% byweight or less, and still more preferably 98% by weight or less. Whenthe proportion of the ionic compound is 99% by weight or less, not onlyformation of the porous layer is facilitated, but also the physicalstrength can be imparted to the porous layer. On the other hand, fromthe viewpoint of further enhancing the physical strength of the porouslayer, the proportion being 50% by weight or less is preferable, theproportion of 45% by weight or less is more preferable, and theproportion of 40% by weight or less is furthermore preferable.

The proportion of the ionic compound in the entire separator forelectricity storage devices is preferably 5% by weight or more, morepreferably 10% by weight or more, and still more preferably 15% byweight or more. When the proportion of the ionic compound in the entireseparator is 5% by weight or more, the heat resistance of the separatortends to be improved. Moreover, this proportion is preferably 95% byweight or less, more preferably 90% by weight or less, and still morepreferably 85% by weight or less. If the proportion of the ioniccompound in the entire separator is 95% by weight or less, fall off ofthe ionic compound from the separator tends to be preventable.

Since the specific gravity of the ionic compound is generally higherthan the specific gravity of the polyolefin resin, it may also be moreappropriate to denote the proportion of the ionic compound in theseparator as % by volume rather than % by weight. The aforementionedproportion is preferably 2% by volume or more to 90% by volume or less,more preferably 5% by volume or lore and 80% by volume or less, andstill more preferably 8% by volume or more and 70% by volume or less.When the proportion of the ionic compound is 2% by volume or more, theheat resistance of the separator tends to be improved. Moreover, when itis 90% by volume or less, fall off of the ionic compound from theseparator tends to be preventable.

An average particle size of the ionic compound is preferably 5 nm ormore and 600 nm or less, more preferably 10 nm or more and 500 nm orless, and still more preferably 20 nm or more and 400 nm or less. Theaverage particle size refers to an average value of particle sizes of 10ionic compounds which can be confirmed in a visual field image when theporous layer is observed at magnification of 30,000× using a scanningelectron microscope. When calculating the average particle size, theparticle size of each particle being present in the form of singleparticle, is used, and if the particles are aggregated, the particlesize of the primary particle constituting the aggregate can be adopted.

When the average particle size of the ionic compound is 5 nm or more,the membrane thickness and the pore distribution of the separator areuniformed, and the input/output characteristics of the electricitystorage device are improved. Also, when the average particle size is 600nm or less, the pore size of the separator is uniformed, and any largepore portion is hardly formed locally, thereby improving safety of theseparator for electricity storage devices.

<<Separator for Electricity Storage Devices>>

The separator for electricity storage devices has a porous structure inwhich the large number of extremely fine pores gather to form densepercolated pores, thereby capable of exhibiting ion conductivity byimpregnating an electrolytic solution as well as favorable voltageresistance and high physical properties. The separator for electricitystorage devices may be in the form of single layer membrane or amultilayer membrane.

The membrane thickness of the separator for electricity storage devicesis preferably 0.1 μm or more and 100 μm or less, more preferably 1 μm ormore and 50 μm or less, and still more preferably 3 μm or more and 25 μmor less. A membrane thickness of 0.1 μm or more is preferable from theviewpoint of mechanical strength, and a membrane thickness of 100 μm orless is preferable from the viewpoint of increasing a battery capacity.The membrane thickness of the separator can be adjusted by controllingthe die lip gap, the stretching ratio in the stretching step, etc.

The average pore size of the separator for electricity storage devicesis preferably 10 nm or more and 100 nm or less, more preferably 20 nm ormore and 90 nm or less, still more preferably 30 nm or more and 80 nm orless, and particularly preferably 40 nm or more and 70 nm or less fromthe viewpoint of ion conductivity and voltage resistance. The averagepore size can be adjusted by controlling the composition ratio, coolingrate of an extruded sheet, stretching temperature, stretching ratio,heat setting temperature, stretching ratio during heat setting,relaxation ratio during heat setting, or by combining thereof.

The average pore size can be measured by a gas-liquid method.Specifically, it has been known that a fluid inside a capillary followsthe Knudsen flow when the mean free path of the fluid is larger than thepore size of the capillary, and when it is smaller, the fluid followsthe Poiseuille flow. Then, it is assumed that the flow of air followsthe Knudsen flow in measurement of the air permeability of theseparator, and the flow of water follows the Poiseuille flow in themeasurement of water permeability.

In this case, the average pore size d (μm) of the porous membrane andthe tortuosity factor τ_(a) (dimensionless) are calculated with the airpermeation rate constant R_(gas) (m³/(m²·second·Pa)), the waterpermeation rate constant R_(liq) (m³/(m²·second·Pa)), molecular velocityof air ν (m/second), viscosity of water η (Pa·second), standard pressureP_(s) (=101325 Pa), porosity ε (%), membrane thickness L (μm), accordingto the following equation:

d=2ν×(R _(liq) /R _(gas))×(16η/3P _(s))×10⁶

τa=(d×(ε/100)×ν/(3L×P _(s) ×R _(gas)))^(1/2)

Here, R_(gas) was determined from the air permeability (second) usingthe following equation:

R _(gas)=0.0001/(air permeability×(6.424×10⁻⁴)×(0.01276×101325))

Also, R_(liq) was determined from the water permeability(cm³/(cm²·second·Pa)) using the following equation:

R _(liq)=water permeability/100

Here, the water permeability was determined as follows. A separatorpreviously immersed in ethanol was set in a stainless steel cell with adiameter of 41 mm for liquid permeation, and after the ethanol in theseparator was washed with water, water was allowed to permeate with adifferential pressure of about 50000 Pa. From the amount (cm³) of thewater permeated for 120 seconds, the water permeability per unittime·unit pressure·unit area, was calculated, which was taken as thewater permeability.

Also, ν was calculated with the gas constant R (=8.314 J/(K·mol)),absolute temperature T (K), circumferential ratio π, and averagemolecular weight of air M (=2.896×10⁻² kg/mol), using followingequation:

ν=((8R×T)/(π×M))^(1/2)

The porosity of the separator for electricity storage devices ispreferably 25% or more to 95% or less, more preferably 30% or more to85% or less, still more preferably 35% or more to 75% or less, andparticularly preferably 40% or more to 65% or less. A porosity of 25% ormore is preferable from the viewpoint of improving ion conductivity, andthe porosity of 95% or less is preferable from the viewpoint of voltageresistance. The porosity of the separator may be adjusted by controllingthe mixing ratio of the polyolefin resin composition and theplasticizer, stretching temperature, stretching ratio, heat settingtemperature, stretching ratio during heat setting, relaxation ratioduring heat setting, or by combining these properties.

The air permeability of the separator for electricity storage devices ispreferably 10 seconds/100 ml or longer and 500 seconds/100 ml orshorter, more preferably 20 seconds/100 ml or longer and 400 seconds/100ml or shorter, still more preferably 30 seconds/100 ml or longer and 300seconds/100 ml or shorter, and particularly preferably 40 seconds/100 mlor longer and 200 seconds/100 ml or shorter. When the air permeabilityis 10 seconds/100 ml or longer, the self-discharge tends to be reducedwhen used as a separator for electricity storage devices, and when it is500 seconds/100 ml or shorter, favorable input/output characteristicstends to be obtainable, which is preferable.

The puncture strength of the separator for electricity storage devicesis preferably 100 gf or more, more preferably 200 gf or more, still morepreferably 300 gf or more, preferably 600 gf or less, more preferably500 gf or less, and still more preferably 400 gf or less. Adjusting thepuncture strength to 100 gf or more is preferable from the viewpoint ofsuppressing membrane rupture due to the active material, etc. thatdropped off when the membrane is wound into a battery, and is alsopreferable to reduce concern for short circuit due to swelling andshrinkage of electrodes accompanied by charge and discharge. On theother hand, it is preferable to adjust the puncture strength to 600 gfor less from the viewpoint allowing to reduce shrinkage due toorientation relaxation when heating.

The viscosity-average molecular weight of the polyolefin resin comprisedin the separator for electricity storage devices is preferably 200,000or more and 5,000,000 or less, more preferably 300,000 or more and3,000,000 or less, and still more preferably 400,000 or more and1,000,000 or more. When the viscosity-average molecular weight is200,000 or more, the melt tension in melt molding is increased, therebyimproving moldability, and there is a likelihood of high strength due toentanglement between polyolefin resins. When the viscosity-averagemolecular weight is 5,000,000 or less, which facilitates melt-kneadinguniformly, and the sheet tends to be excellent in moldability,particularly thickness stability. Furthermore, when used as a separatorfor electricity storage devices, if the viscosity-average molecularweight of the separator is less than 1,000,000, pores have a likelihoodof being clogged when a temperature rises, which is preferable because afavorable fuse function tends to be obtainable.

The degree of whiteness of the separator for electricity storage devicesis more than 98.0 and 105 or less, preferably 98.5 or more and 104 orless, and more preferably 99 or more and 103 or less. When the degree ofwhiteness of the separator is more than 98.0, the deterioration of thepolyolefin is small, so that the reliability and safety of theelectricity storage device can be improved. When the degree of whitenessof the separator is 105 or less, it is preferable from the viewpoint ofpractical use because a separator in which the polyolefin is lessdeteriorated can be efficiently manufactured.

The degree of whiteness is measured using a colorimeter “SC-T”(manufactured by Suga Test Instruments Co., Ltd.) under a condition thatdoes not include a specular reflection light in a 2° viewing angle. Whenthe thickness of the separator is 20 μm or less, the color of the backsurface of the separator surface that is to be detected may be detected,which leads to incorrect measurement of the degree of whiteness of theseparator. Therefore, when the thickness of the separator is 20 um orthinner, the degree of whiteness is defined as the one that is measuredunder the condition with the separator that is folded to the totalthickness of 20 μm or more.

The voltage resistance of the separator for electricity storage devicescan be measured using a voltage resistance/insulation resistance tester(TOS 9201, manufactured by Kikusui Electronics Co., Ltd.). Specifically,for example, the separator is sandwiched by smooth metal plates, andvoltage is applied and increased at a speed of 1 kV/second, followed bymeasurement of a voltage value at which a short circuit is detected (AC60 Hz). When comparing the voltage resistance value of the separatorhaving a different thickness, it is possible to compare the intrinsicvoltage resistance value normalized in terms of separator thickness, andtherefore in the Examples described later, each separator is compared bycalculating the voltage resistance value that is converted to that perthickness of 20 μm. The voltage resistance (kV/20 μm) per 20 μm ispreferably 1.3 kV/20 μm or more, more preferably 1.4 kV/20 μm or moreand still more preferably 1.5 kV/20 μm or more from the viewpoint ofsuppressing membrane rupture due to an active material, etc., thatdropped off when fabricating a wound body.

The reason for the suppression of deterioration of the polyolefincomprised in the separator for electricity storage devices of thepresent embodiment is not necessarily clarified and is not limited tothe action or principle described in this paragraph, however, it isconjectured because a filler not inducing deterioration is used in theseparator of the present embodiment. As one of methods for preparingfine particles of metal oxides such as silica, etc., a method(combustion method) for hydrolyzing SiCl₄ at an elevated temperature hasbeen known. In this case, it is surmised that since it is difficult tocompletely remove hydrogen chloride by-produced, deterioration of thepolyolefin is promoted by the remaining acidic component. On the otherhand, for ionic compounds, a chemical synthesis method such ascoprecipitation method is often used for producing fine particles. Thechemical synthesis method has a likelihood to reduce the amount ofimpurities compared to the method for pulverizing natural ore, and thedeterioration of the polyolefin due to the impurities is considered tohardly occur. It is conjectured to be possible to increase the degree ofwhiteness of the resulting separator to over 98.0 by using an ioniccompound with few impurities.

Furthermore, the separator for electricity storage devices of thepresent embodiment preferably comprises polyethylene having aviscosity-average molecular weight of 600,000 or more from the viewpointof enhancing the degree of whiteness. The reason for the degree ofwhiteness being improved when using the above polyethylene is notnecessarily clear, and is not limited to the action or principledescribed in this paragraph, however, it is conjectured that whencontaining polyethylene having a viscosity-average molecular weight of600,000 or more, the fibril portion constituting the porous layer isdensified as a consequence of a high degree of entanglement of thepolyethylene with the ionic compound, so that the reflected light isunified, consequently giving rise to tendency for the degree ofwhiteness of the separator to be higher.

Namely, when the separator of the present embodiment comprises thepolyolefin resin and the ionic compound in the same layer, and inparticular, comprises polyethylene having a viscosity-average molecularweight of 600,000 or more, a separator having the degree of whiteness ofmore than 98.0 tends to be obtainable, which is preferred.

<<Manufacturing Method of Separator for Electricity Storage Devices>>

Although an example will be described regarding the method formanufacturing the separator for electricity storage devices according tothe present embodiment, it is not necessarily restricted to thisexample. The method for manufacturing the separator may include, forexample, the following steps:

(1) a step of melt-kneading the polyolefin resin, ionic compound, andplasticizer to obtain a kneaded product,(2) a step of transferring the kneaded product, molding it into sheetform, and then cooling and solidifying it,(3) a step of stretching the sheet molding at least in a uniaxialdirection at a stretching ratio by area of 20 times or more and lessthan 200 times, and(4) a step of extracting the plasticizer from the sheet molding afterthe stretching step.

In step (1), the polyolefin resin, ionic compound, and plasticizer aremelt-kneaded. As a melt-kneading method, an example thereof includessuch as feeding the polyolefin resin, the ionic compound and, ifnecessary, other additives into a resin-kneading apparatus such as anextruder, kneader, laboplastmill, kneading roll, Banbury mixer, etc.,and introducing and kneading the plasticizer by arbitrary ratios whileheat-melting the resin components.

Although the plasticizer is not particularly restricted, however, anon-volatile solvent that enables to form a uniform solution above themelting point of polyolefin resin is preferably used. Specific examplesof such a non-volatile solvent include, for example, hydrocarbons suchas liquid paraffin, paraffin wax, etc.; esters such as dioctylphthalate, dibutyl phthalate, etc.; higher alcohols such as oleylalcohol, stearyl alcohol, etc. These plasticizers may be recovered byoperations such as distillation, etc., after the extraction, and may bereused. Furthermore, the polyolefin resin, ionic compound, otheradditives, and plasticizer are preferably preliminarily kneaded at aprescribed proportion thereof using a Henschel mixer, etc., beforeintroduced into a resin-kneading apparatus. More preferably, in thepre-kneading, the plasticizer is partially introduced, and the remainingplasticizer is kneaded while being appropriately heated and side-fed tothe resin kneading apparatus. By using such a kneading method, thedispersibility of the plasticizer is enhanced, and when stretching asheet molding of the melt-kneaded product of the resin composition andthe plasticizer in a later step, the sheet molding tends to bestretchable at a high ratio without rupture of the membrane.

Among the plasticizers, liquid paraffin is preferable because in thecase that the polyolefin resin is polyethylene or polypropylene, theliquid paraffin is highly compatible with these, and even if themelt-kneaded product is stretched, interfacial stripping between theresin and the plasticizer hardly occurs, facilitating to implementuniform stretching.

The proportion of the polyolefin resin, the ionic compound, and theplasticizer is not particularly limited provided these can bemelt-kneaded uniformly and molded into sheet form. For example, theweight fraction of the plasticizer in the composition composed of thepolyolefin resin, the ionic compound, and the plasticizer is preferably10 to 90% by weight, and more preferably 20 to 80% by weight. When theweight fraction of the plasticizer is 90% by weight or less, the melttension during melt—molding tends to be sufficient for improvingmoldability. On the other hand, when the weight fraction of theplasticizer is 10% by weight or more, no scission of the polyolefinmolecular chains takes place even when the mixture of the polyolefinresin composition and the plasticizer is stretched at a high ratio,facilitating to form a uniform and microporous structure and also toincrease strength.

In step (2), the melt-kneaded product is formed into sheet form. As amethod for manufacturing a sheet molding, an example thereof includessuch as extruding a melt-kneaded product in sheet from via a T die,etc., bringing the sheet in contact with a heat conductor, and coolingto a temperature sufficiently lower than the crystallization temperatureof the resin component followed by solidification thereof. As a heatconductor used for cooling solidification, a metal, water, air,plasticizer, etc., are included. Among these, a metal roll is preferabledue to high heat conduction efficiency thereof. Also, when the extrudedkneaded-product is subjected to contact with the metal roll, it ispreferable to sandwich it between the rolls, from which not only theefficiency of heat conduction is further increased, but also themembrane strength is increased due to orientation of the sheet, whichfurther tends to improve the surface smoothness of the sheet. The dielip gap when extruding the melt-kneaded product in sheet form from theT-die is preferably 200 μm or more to 3,000 μm or less, and morepreferably 500 μm or more and 2,500 μm or less. When the die lip gap is200 μm or more, the resin waste, etc., are reduced, the influence onmembrane quality such as streaks and defects is small, and the risk ofmembrane rupture, etc., can be reduced in the subsequent stretchingstep. On the other hand, when the die lip gap is 3,000 μm or less, thecooling rate is fast, which enables to prevent cooling unevenness, andthe thickness stability of the sheet can be maintained.

Also, the sheet molding may be subjected to rolling. The rolling can becarried out by, for example, a press method using a double belt pressmachine, etc. By the rolling, the orientation of in particular, thesurface layer portion can be promoted. The rolling ratio by area ispreferably more than one time and three times or less, and morepreferably more than one time and two times or less. When the rollingratio is more than one time, the plane orientation tends to be increasedand the membrane strength of the finally obtained separator tends to beincreased. On the other hand, when the rolling ratio is three times orless, the difference in orientation between the surface layer portionand the inside of the center is small, which tends to facilitateformation of a uniform porous structure in a thickness direction of themembrane.

In step (3), the aforementioned sheet molding is subjected tostretching. Stretching may also be carried out after extracting theplasticizer from the sheet molding. Furthermore, it may also be carriedout before and after extracting the plasticizer from the aforementionedsheet molding.

Although either uniaxial stretching or biaxial stretching can besuitably applied as the stretching treatment, biaxial stretching ispreferable from the viewpoint of improving the strength of the obtainedseparator. Upon biaxial stretching of the sheet molding at a highstretching ratio, the molecules are oriented in a plane direction, andthe separator finally obtained hardly tears and has high puncturestrength. Examples of the stretching method include such as simultaneousbiaxial stretching, sequential biaxial stretching, multistagestretching, multiple-time stretching, etc. Simultaneous biaxialstretching is preferable from the viewpoint of improvement on puncturestrength, stretching uniformity, and fuse characteristics. Further, fromthe viewpoint of controllability of plane orientation, sequentialbiaxial stretching is preferred.

Here, simultaneous biaxial stretching refers to a stretching method inwhich MD (machine direction of continuous separator processing)stretching and TD (transverse direction crossing the MD of the separatorat an angle of 90°) are simultaneously carried out, and the stretchingratio in each direction may be different. Sequential biaxial stretchingis referred to as a stretching method in which MD stretching and TDstretching are each carried out independently, and upon MD stretching orTD stretching, the other direction is in a non-constrained state or inanchored state with fixed length.

The stretching ratio is preferably in the range of 20 times or more and200 times or less in terms of a ratio by area, and more preferably inthe range of 25 times or more and 150 times or less. The stretchingratio in each axial direction is preferably 4 times or more and 15 timesor less in MD and 4 times or more and 15 times or less in TD, and morepreferably 5 times or more and 12 times or less in MD and 5 times ormore and 12 times or less in TD. When the total ratio by area is 25times or more, sufficient strength tends to be imparted to the obtainedseparator, while when the total ratio by area is 200 times or less,membrane rupture during the stretching step is prevented and highproductivity tends to be achieved.

In step (4), the plasticizer is removed from the sheet molding to form aseparator. As a method for removing the plasticizer, an example thereofincludes such as immersing the sheet molding in an extraction solvent toextract the plasticizer followed by fully drying. The plasticizer may beextracted either batchwise or continuously. In order to suppress theshrinkage of the separator, it is preferable to constrain the edges ofthe sheet molding in a series of steps such as immersion and drying.Moreover, it is preferable to adjust the amount of residual plasticizerin the separator to less than 1% by weight with respect to the weight ofthe entire separator.

As an extraction solvent used when extracting a plasticizer, it ispreferable to use a solvent which is a poor solvent for the polyolefinresin and a good solvent for the plasticizer and has a boiling pointlower than the melting point of the polyolefin resin. Examples of suchextraction solvents include hydrocarbons such as n-hexane, cyclohexane,etc.; halogenated hydrocarbons such as methylene chloride,1,1,1-trichloroethane, etc.; non-chlorinated halogenated solvents suchas hydrofluoroether, hydrofluorocarbon, etc.; alcohols such as ethanol,isopropanol, etc.; ethers such as diethyl ether, tetrahydrofuran, etc.;and ketones such as acetone, methyl ethyl ketone, etc. These extractionsolvents may be recovered by operations such as distillation, etc., andmay be reutilized.

In order to suppress shrinkage of the separator, heat treatment can alsobe carried out with the aim of heat setting after the stretching step orafter formation of the separator. Moreover, the separator may besubjected to post-treatments such as hydrophilization treatment with asurfactant, etc., crosslinking treatment with an ionizing radiation,etc.

The separator is preferably subjected to heat treatment for the purposeof heat setting from the viewpoint of suppressing the shrinkage. As amethod of heat treatment, with the aim of adjusting physical properties,examples of the heat treatment include stretching operation carried outat a prescribed temperature atmosphere and prescribed stretching ratio,and/or relaxation operation carried out at a prescribed temperatureatmosphere and prescribed relaxation ratio for the purpose of reductionof stretching stress. The relaxation operation may be carried outfollowing the stretching operation. These heat treatments can be carriedout using a tenter or a roll stretcher.

The stretching operation is preferably carried out by stretching 1.1times or more, more preferably 1.2 times or more in MD and/or TD of themembrane, from the viewpoint of obtaining a separator with higherstrength and higher porosity. The relaxation operation is a shrinkingoperation in MD and/or TD of the membrane. The relaxation ratio isreferred to as a value obtained by dividing the dimension of themembrane after the relaxation operation by the dimension of the membranebefore the relaxation operation. When relaxation was carried out in bothMD and TD, the relaxation ratio means a value obtained by multiplyingthe relaxation ratio of MD and the relaxation ratio of TD. Therelaxation ratio is preferably 1.0 or less, more preferably 0.97 orless, and still more preferably 0.95 or less. The relaxation ratio ispreferably 0.5 or more from the viewpoint of membrane quality. Therelaxation operation may be carried out in both MD and TD, however, maybe carried out in either MD or TD.

The stretching and relaxation operations after this plasticizerextraction are preferably carried out in TD. In contrast to the meltingpoint (hereinafter also referred to as “Tm”) of the polyolefin resin,the temperature of the stretching and relaxation operations ispreferably Tm−20° C. or higher and Tm+20° C. or lower, and morepreferably Tm−10° C. or higher and Tm+10° C. or lower. The temperatureof the stretching and relaxation operations in the aforementioned rangeis preferred from the viewpoint of the balance of reduction of heatshrinkage and the porosity.

When the separator is fabricated by a “wet method” for forming pores byplasticizer extraction, the pore size, pore shape, and distribution ofthe position of the pores are easily equalized, as a result, thereflected light of the separator is uniformed, and thereby the degree ofwhiteness of the separator tends to be high. Therefore, from theviewpoint of increasing the degree of whiteness of the separator togreater than 98.0, it is preferable to carry out the method of poreformation by the plasticizer extraction.

The separator for electricity storage devices of the present embodimentitself functions sufficiently as a separator for electricity storagedevices, but if necessary, a surface of the separator may be coated withan inorganic material and/or organic material to form a laminatedmembrane. The separator for electricity storage devices of the presentembodiment has high heat resistance with less deterioration inpolyolefin, thereby improving reliability and safety of the electricitystorage device.

<<Electricity Storage Device>>

The electricity storage device of the present embodiment is providedwith a positive electrode, negative electrode, and the separator forelectricity storage devices according to the present embodiment.Specific examples of the electricity storage device include a lithiumsecondary battery, lithium ion secondary battery, sodium secondarybattery, sodium ion secondary battery, magnesium secondary battery,magnesium ion secondary battery, calcium secondary battery, calcium ionsecondary battery, aluminum secondary battery, aluminum ion secondarybattery, nickel metal hydride battery, nickel cadmium battery, electricdouble layer capacitor, lithium ion capacitor, redox flow battery,lithium sulfur battery, lithium air battery, zinc air battery, etc.Among the aforementioned batteries, from the viewpoint of practicality,a lithium secondary battery, lithium-ion secondary battery, nickel metalhydride battery, or lithium ion capacitor is preferable, and a lithiumion secondary battery is more preferable.

The electricity storage device of the present embodiment can befabricated by combining the positive electrode and the negativeelectrode described above via the separator, winding as necessary toform a laminated electrode body or a wound electrode body, loading itinto an outer package, connecting the positive and negative electrodesto positive and negative electrode terminals of the outer package via alead, etc., and further injecting a nonaqueous electrolytic solutioncontaining a nonaqueous solvent such as cyclic carbonate or linearcarbonate, etc., and an electrolyte such as lithium salt, etc., into theouter package, followed by sealing the outer package.

The outer package of the electricity storage device is not particularlylimited, but a metal can container, a laminate container composed of ametal foil laminate film, etc., can be suitably used. The shape of thestorage device is not particularly limited, and for example, acylindrical, square, coin type, flat, or sheet may be employed.

<<Positive Electrode>>

The positive electrode is prepared by adding appropriate amounts of aconductive assistant such as acetylene black, etc., and binders such aspolyvinylidene fluoride, etc., to a positive electrode active materialto prepare a positive electrode mixture, coating a current collectorsuch as an aluminum foil, etc., with the mixture followed by drying, andthen applying pressure to adhere the positive electrode mixture layer onthe current collector. It is note that the method for preparing thepositive electrode is not limited to the method exemplified above.

The positive electrode active material is not particularly restricted,but from the viewpoint of structural stability of the positive electrodeactive material, it is preferably complex oxide of a layered oxidecathode active material represented by the chemical formula:LiNi_(x)Co_(y)Ma_(1-x-y)O₂ wherein, Ma represents one or more selectedfrom the group consisting of Mn and Al, 0≤x≤1, 0≤y≤1, and x+y≤1; aspinel-type oxide cathode active material represented by the chemicalformula: LiMn_(2-x)Mb_(x)O₄ wherein, Mb represents one or more selectedfrom the group consisting of transition metals, and 0.2≤x≤0.7; Li₂McO₃and LiMdO₂ wherein, Mc and Md each independently represent one or moreselected from the group consisting of transition metals, and one or morepositive electrode active materials selected from the group consistingof a Li-rich layered oxide cathode material represented by the chemicalformula: zLi₂McO₃-(1-z)LiMdO₂ wherein Mc and Md each independentlyrepresent one or more selected from the group consisting of transitionmetals, and 0.05≤z≤0.95; olivine-type cathode active materialrepresented by LiMe_(1-x)Fe_(x)PO₄ wherein, Me represents one or moreselected from the group consisting of Mn and Co, and 0≤x≤1, andLi₂MfPO₄F wherein, Mf represents one or more selected from the groupconsisting of transition metals, are included.

As the layered oxide cathode active material represented by the chemicalformula: LiNi_(x)Co_(y)Ma_(1-x-y)O₂ wherein, Ma represents one or moreselected from the group consisting of Mn and Al, 0≤x≤1, 0≤y≤1, and x+y≤1from the viewpoint of the structural stability, it preferably has acomposition represented by LiNi_(x)Co_(y)Mn_(1-x-y)O₂ wherein, 0≤x≤1,0≤y≤1 and x+y≤1 or LiNi_(x)Co_(y)Al_(1-x-y)O₂ wherein, 0.7≤x≤1, 0≤y≤0.3,and x+y≤1. As more preferable compositions, LiCoO₂,LiNi_(x)Co_(y)Mn_(1-x-y)O₂ wherein, 0.3≤x≤1, 0≤y≤0.4, and x+y≤1 andLiNi_(0.85)Co_(0.1)Al_(0.05)O₂, are included.

<<Negative Electrode>>

The negative electrode is prepared by adding appropriate amounts of athickener such as carboxymethyl cellulose, etc., and a binder such asstyrene butadiene rubber, etc., to a negative electrode active materialto prepare a negative electrode mixture, coating a current collectorsuch as a copper foil, etc., with the mixture followed by drying, andthen applying pressure to adhere the negative electrode mixture layer onthe current collector. It is noted that the method for preparing thenegative electrode is not limited to the method exemplified above.

In the present embodiment, the negative electrode active material thatcan be used for the negative electrode is not particularly limited,however, alloy compounds such as Al, Si, Sn, etc.; metal oxides such asCuO, CoO, etc.; lithium-containing compounds such as lithium titanate,etc.; carbon materials, etc., may be used. From the viewpoint ofimproving the energy density of the electricity storage device, a carbonmaterial capable of intercalating and releasing lithium ions at arelatively low potential is preferred. Such a carbon material is notparticularly restricted, however, examples thereof include hard carbon,soft carbon, artificial graphite, natural graphite, pyrolytic carbon,coke, glassy carbon, burning product of an organic polymer compound, andburning products of an organic natural product, carbon fiber, mesocarbonmicrobeads, carbon black, etc.

When the carbon material is used as the negative electrode activematerial, the interlayer distance d₀₀₂ of (002) plane of the carbonmaterial is preferably 0.37 nm or less, more preferably 0.35 nm or less,and still more preferably 0.34 nm or less. The lower limit of d₀₀₂ isnot particularly restricted but is theoretically about 0.335 nm. Thesize of the crystallite in the c-axis direction of the carbon materialis preferably 3 nm or more, more preferably 8 nm or more, and still morepreferably 25 nm or more. Although the upper limit of the size of thecrystallite is not particularly limited, it is generally about 200 nm.Moreover, the average particle size of the carbon material is preferably3 μm or more and 15 μm or less, more preferably 5 μm or more and 13 μmor less. Also, the purity of the carbon material is preferably 99.9% orhigher.

The electricity storage device of the present embodiment is excellent insafety and productivity, and therefore it is not only suitable for useas an automotive battery, but also widely utilized as power sources forvarious appliances including batteries for customer appliances such assmartphones, etc.

EXAMPLES

The present embodiments will be described below in more detail by way ofExamples, and the present invention is not limited to the Examplesunless the present invention depart from the scope of the gist thereof.It is noted that the analytical method and evaluation methods used inExamples and Comparative Examples are as described below.

(1) Membrane Thickness (μm)

The membrane thickness of the sample was measured at a room temperatureof 23° C. using a micro thickness gauge (type KBM, manufactured by ToyoSeiki Seisaku-sho, Ltd.).

(2) Porosity (%)

A 10 cm×10 cm square sample was cut out from the separator, the volume(cm³) and weight (g) of the sample were measured, and the porosity wascalculated from these and the membrane density (g/cm³) using thefollowing equation:

Porosity (%)=(volume−weight/membrane density)/volume×100

It is noted that the membrane density was used as the value calculatedfrom each density of the polyolefin resin and the ionic compound, andthe mixing ratio thereof.

(3) Air Permeability (second/100 ml)

Air permeability of a sample was measured using a Gurley type airpermeability tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.),according to HS P-8117.

(4) Puncture Strength (gf)

A separator was set with a sample holder having an opening diameter of11.3 mm, using a handy compression tester “KES-G5” (manufactured by KatoTech Co., Ltd). Subsequently, a puncture test was carried out bycontacting the center of the set separator and a needle tip withcurvature radius of 0.5 mm under conditions with a puncture speed of 2mm/second and an atmospheric temperature of 25° C., and the puncturestrength (gf) was obtained as the maximum puncture load.

(5) Degree of Whiteness

The degree of whiteness was measured using a colorimeter “SC-T”(manufactured by Suga Test Instruments Co., Ltd.). When the thickness ofthe separator was less than 20 μm, the separator was folded and adjustedto the total thickness of 20 μm or more, and the degree of whiteness wasmeasured under a condition that does not include a specular reflectionlight in a 2° viewing angle.

(6) Voltage Resistance (kV/20 μm)

Using a voltage resistance/insulation resistance tester “TOS9201”(manufactured by Kikusui Electronics Co., Ltd.), the separator wassandwiched by smooth metal plates, and voltage was applied and increasedat a speed of 1 kV/second, followed by measurement of a voltage value atwhich a short circuit was detected (AC 60 Hz). The obtained voltagevalue was converted to a voltage resistance value (kV/20 μm) per 20 μmaccording to the following equation.

Voltage resistance (kV/20 μm)=voltage measurement value (kV)×20/membranethickness (μm)

(7) Solder Test (mm²)

A soldering iron having a tip diameter of 1 mm was placed vertically tothe separator fixed to a frame. The temperature of the soldering ironwas raised to 400° C., and after the temperature was stabilized, thesoldering iron was lowered at a speed of 10 mm/second and puncturedthrough the separator for 3 seconds followed by elevation of the iron.The area of the hole of the separator was observed with an opticalmicroscope, and the area was determined by image processing.

(8) Tests Using Lithium Ion Secondary Battery <<Fabrication of PositiveElectrode Sheet>>

A slurry solution was prepared by mixing LiNi_(1/3)Mn_(1/3)CO_(1/3)O₂(manufactured by Nippon Chemical Industrial Co., Ltd.) as the positiveelectrode active material, an acetylene black powder (manufactured byDenka Co., Ltd.) as the conductive assistant, and a polyvinylidenedifluoride solution (manufactured by KUREHA CORPORATION) as the binderat a solid content ratio by weight of 90/6/4, and addingN-methyl-2-pyrrolidone as a dispersion solvent to a solid content byweight of 40% followed by further mixing. Both sides of a 20 μm thickaluminum foil were coated with the slurry solution, the solvent wasremoved by drying, and thereafter, the coated aluminum foil was rolledwith a roll press to obtain a positive electrode sheet.

<<Preparation of Negative Electrode Sheet>>

A slurry solution was prepared by mixing a graphite powder (Osaka GasChemicals Co., Ltd.) as the negative electrode active material, astyrene butadiene rubber and a carboxymethylcellulose aqueous solutionas the binders at a solid content ratio by weight of 100/1.5/1.8, andadding water as a dispersion solvent to a solid content by weight of 45%followed by further mixing. Both sides of an 18 μm thick copper foilwere coated with the slurry solution, the solvent was removed by drying,and thereafter, the coating copper foil was rolled with a roll press toobtain a negative electrode sheet.

<<Preparation of Nonaqueous Electrolytic Solution>>

LiPF₆ was contained at 1 mol/L in a mixed solvent in which ethylenecarbonate and ethyl methyl carbonate as nonaqueous solvents were mixedat a volume ratio of 1:2 to prepare the solution.

<<Fabrication of Lithium Ion Secondary Battery>>

The positive electrode sheet and the negative electrode sheet asprepared in the manner described above were each combined on each sideof the separator obtained in the Examples and Comparative Examplesdescribed below to form a laminate. The obtained laminate was insertedinto a package (outer package) composed of an aluminum laminate film inwhich both surfaces of an aluminum foil (thickness of 40 μm) werecovered with resin layers, with positive and negative electrodeterminals being protruded from the package. Thereafter, the nonaqueouselectrolytic solution as prepared in the manner described above wasinjected into the outer package, and the package was subjected to vacuumsealing to fabricate a Pouch type lithium ion secondary battery.

<<Initial Charge and Discharge of Lithium Ion Secondary Battery>>

The Pouch type lithium ion secondary battery was housed in athermostatic chamber “PLM-735” (manufactured by Futaba K. K.) set at 25°C. and connected to a charge/discharge apparatus “ACD-01” (manufacturedby Aska Electronic Co., Ltd.). Next, the charge and discharge cyclewherein the secondary battery was charged with a constant current of 0.1C until the voltage reached 4.2V, then charged with a constant voltageof 4.2V for 1 hour, and discharged down to 3.0V with a constant currentof 0.1C, was repeated three times. Thereafter it was charged with aconstant current of 0.1C until the voltage reached 4.2V to complete fullcharge of the lithium ion battery. In this regard, 1C is defined as acurrent value with which a battery is discharged to full capacity in 1hour, and 0.1C denotes 1/10 thereof.

<<20C Discharge Tests of Lithium Ion Secondary Battery>>

The Pouch type lithium ion secondary battery after the initialcharge/discharge was housed in a thermostatic chamber “PLM-735”(manufactured by Futaba K. K.) set at 25° C. and connected with acharge/discharge apparatus “ACD-01” (manufactured by Aska ElectronicCo., Ltd.). Next, the secondary battery was charged with a constantcurrent of ⅓C until the voltage reached 4.2V, thereafter charged with aconstant voltage of 4.2V for one hour and discharged down to 3.0V with aconstant current of 1C. Subsequently, it was charged with a constantcurrent of ⅓C until the voltage reached 4.2V, charged with a constantvoltage of 4.2V for one hour, and discharged down to 3.0V with aconstant current of 20C. From the results on the series ofcharge/discharge described above, the 20C capacity retention ratio wascalculated according to the equation below:

20C capacity retention ratio (%)=20C discharging capacity/1C dischargingcapacity×100

<<Cycle Tests of Lithium Ion Secondary Battery>>

The Pouch type lithium ion secondary battery after 20C discharge testswas housed in a thermostatic chamber “LM-73S” (manufactured by Futaba K.K.) set at 50° C. and connected with a charge/discharge apparatus“ACD-01” (manufactured by Aska Electronic Co., Ltd.). Next, thesecondary battery was charged at a constant current of 1C until thevoltage reached 4.2V, thereafter charged with a constant voltage of 4.2Vfor one hour and discharged down to 3.0V with a constant current of 1C.The series of charge/discharge described above was defined as 1 cycle.Then, 100 cycles were carried out and the capacity retention ratio (%)after the 100 cycles was measured. Here, the capacity retention ratio(%) after 100 cycles was obtained according to the equation below:

Capacity retention ratio (%) after 100 cycles=discharging capacity at100 cycles/discharging capacity at 1 cycle×100

The materials used in Examples and Comparative Examples are as follows.

-   -   (1) Polyolefin resin

Polyethylene A (UH650, manufactured by Asahi Kasei Corporation) having aviscosity-average molecular weight of 700,000 and a melting point of135° C.

Polyethylene B (7000 FP, manufactured by Prime Polymer Co., Ltd.) havinga viscosity-average molecular weight of 260,000 and a melting point of131° C.

Polyethylene C (UH850, manufactured by Asahi Kasei Corporation) having aviscosity-average molecular weight of 2,000,000 and a melting point of135° C.

(2) Ionic Compounds and Metal Oxides

Barium sulfate (coprecipitation method) with an average particle size of10 nm

Barium sulfate (coprecipitation method) with an average particle size of50 nm

Barium sulfate (ore pulverizing method) with an average particle size of660 nm

Sodium phosphate (coprecipitation method) with an average particle sizeof 500 nm

Aluminum sulfate (coprecipitation method) with an average particle sizeof 800 nm

Lithium fluoride with an average particle size of 30 nm

Silica (combustion method) with an average particle size of 16 nm

Alumina (combustion method) with an average particle size of 10 nm

Boehmite (hydrothermal synthesis method) with an average particle sizeof 800 nm

Potassium titanate with an average particle size of 400 nm

(3) Plasticizer

Liquid paraffin with a kinetic viscosity of 70.6cSt at 40° C.

(4) Antioxidants

Tetrakis-[methylene-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane

Example 1

Polyethylene A (85 parts by weight), barium sulfate (15 parts by weight)having an average particle size of 50 nm, and an antioxidant (0.85 partsby weight) were dry-blended with a Henschel mixer to obtain a mixed rawmaterial.

The mixed raw material was fed by a feeder to a twin-screw extruderunder a nitrogen atmosphere. Also, liquid paraffin was injected into theextruder cylinder by a plunger pump. The operating conditions of thefeeder and pump were adjusted so that the proportion of liquid paraffinwas 66 parts by weight and the proportion of the sum of the polymer andionic compound was 34 parts by weight in the total mixture extruded.Then, these were melt-kneaded while heating to 200° C. in a twin-screwextruder, and the resulting melt-kneaded product was extruded through aT-die onto a cooling roll controlled to a surface temperature of 90° C.The product was brought into contact with the cooling roll, molded andsolidified by cooling to obtain a sheet molding.

The sheet molding was stretched at a temperature of 122° C. at astretching ratio of 7×6.4 times with a simultaneous biaxial stretchingmachine, and the stretched product was immersed in methylene chloride toextract and remove liquid paraffin, and then dried. Next, the obtainedstretched sheet was stretched 1.8 times in a width direction at atemperature of 134° C. using a uniaxial stretching machine, and then thestretched sheet was relaxed about 20% in the width direction to obtain aseparator. The evaluation results of the obtained separator are shown inTable 1.

Example 2

A separator was fabricated in the same manner as in Example 1 with theexception of using mixed raw materials obtained by dry-blendingpolyethylene A (70 parts by weight), barium sulfate (30 parts by weight)having an average particle size of 50 nm, and the antioxidant (0.7 partsby weight) using a Henschel mixer, in place of the mixed raw materialsof Example 1. The evaluation results of the obtained separator are shownin Table 1.

Example 3

A separator was fabricated in the same manner as in Example 1 with theexception of using mixed raw materials obtained by dry-blendingpolyethylene A (40 parts by weight), barium sulfate (60 parts by weight)having an average particle size of 50 nm, and the antioxidant (0.4 partsby weight) using a Henschel mixer, in place of the mixed raw material ofExample 1. The evaluation results of the obtained separator are shown inTable 1.

Example 4

A separator was fabricated in the same manner as in Example 1 with theexception of using mixed raw materials obtained by dry-blendingpolyethylene A (20 parts by weight), barium sulfate (80 parts by weight)having an average particle size of 50 nm, and the antioxidant (0.2 partsby weight) using a Henschel mixer, in place of the mixed raw materialsof Example 1. The evaluation results of the obtained separator are shownin Table 1.

Example 5

A separator was fabricated in the same manner as in Example 1 with theexception of using barium sulfate having an average particle size of 10nm in place of barium sulfate having an average particle size of 50 nmof Example 1. The evaluation results of the obtained separator are shownin Table 1.

Example 6

A separator was fabricated in the same manner as in Example 2 with theexception of using barium sulfate having an average particle size of 10nm in place of barium sulfate having an average particle size of 50 nmof Example 2. The evaluation results of the obtained separator are shownin Table 1.

Example 7

A separator was fabricated in the same manner as in Example 3 with theexception of using barium sulfate having an average particle size of 10nm in place of barium sulfate having an average particle size of 50 nmof Example 3. The evaluation results of the obtained separator are shownin Table 1.

Example 8

A separator was fabricated in the same manner as in Example 4 with theexception of using barium sulfate having an average particle size of 10nm in place of barium sulfate having an average particle size of 50 nmof Example 4. The evaluation results of the obtained separator are shownin Table 1.

Example 9

A separator was fabricated in the same manner as in Example 4 with theexception of using barium sulfate having an average particle size of 660nm in place of barium sulfate having an average particle size of 50 nmof Example 4. The evaluation results of the obtained separator are shownin Table 1.

Example 10

A separator was fabricated in the same manner as in Example 1 with theexception of using polyethylene B in place of polyethylene A ofExample 1. The evaluation results of the obtained separator are shown inTable 1.

Example 11

A separator was fabricated in the same manner as in Example 1 with theexception of using sodium phosphate having an average particle size of500 nm in place of barium sulfate having an average particle size of 50nm of Example 1. The evaluation results of the obtained separator areshown in Table 1.

Example 12

A separator was fabricated in the same manner as in Example 2 with theexception of using sodium phosphate having an average particle size of500 nm in place of barium sulfate having an average particle size of 50nm of Example 2. The evaluation results of the obtained separator areshown in Table 2.

Example 13

A separator was fabricated in the same manner as in Example 3 with theexception of using sodium phosphate having an average particle size of500 nm in place of barium sulfate having an average particle size of 50nm of Example 3. The evaluation results of the obtained separator areshown in Table 2.

Example 14

A separator was fabricated in the same manner as in Example 4 with theexception of using sodium phosphate having an average particle size of500 nm in place of barium sulfate having an average particle size of 50nm of Example 4. The evaluation results of the obtained separator areshown in Table 2.

Example 15

A separator was fabricated in the same manner as in Example 1 with theexception of using mixes raw materials obtained by dry-blendingpolyethylene C (5 parts by weight), sodium phosphate (95 parts byweight) having an average particle size of 500 nm, and the antioxidant(0.05 parts by weight) using a Henschel mixer, in place of the mixed rawmaterials of Example 1. The evaluation results of the obtained separatorare shown in Table 2.

Example 16

A separator was fabricated in the same manner as in Example 1 with theexception of using aluminum sulfate having an average particle size of800 nm in place of barium sulfate having an average particle size of 50nm of Example 1. The evaluation results of the obtained separator areshown in Table 2.

Example 17

A separator was fabricated in the same manner as in Example 2 with theexception of using aluminum sulfate having an average particle size of800 nm in place of barium sulfate having an average particle size of 50nm of Example 2. The evaluation results of the obtained separator areshown in Table 2.

Example 18

A separator was fabricated in the same manner as in Example 3 with theexception of using aluminum sulfate having an average particle size of800 nm in place of barium sulfate having an average particle size of 50nm of Example 3. The evaluation results of the obtained separator areshown in Table 2.

Example 19

A separator was fabricated in the same manner as in Example 4 with theexception of using aluminum sulfate having an average particle size of800 nm in place of barium sulfate having an average particle size of 50nm of Example 4. The evaluation results of the obtained separator areshown in Table 2.

Example 20

A separator was fabricated in the same manner as in Example 15 with theexception of using aluminum sulfate having an average particle size of800 nm in place of sodium phosphate having an average particle size of500 nm of Example 15. The evaluation results of the obtained separatorare shown in Table 2.

Example 21

A separator was fabricated in the same manner as in Example 1 with theexception of using lithium fluoride having an average particle size of30 nm in place of barium sulfate having an average particle size of 50nm of Example 1. The evaluation results of the obtained separator areshown in Table 2.

Example 22

A separator was fabricated in the same manner as in Example 2 with theexception of using lithium fluoride having an average particle size of30 nm in place of barium sulfate having an average particle size of 50nm of Example 2. The evaluation results of the obtained separator areshown in Table 2.

Example 23

A separator was fabricated in the same manner as in Example 3 with theexception of using lithium fluoride having an average particle size of30 nm in place of barium sulfate having an average particle size of 50nm of Example 3. The evaluation results of the obtained separator areshown in Table 2.

Example 24

A separator was fabricated in the same manner as in Example 4 with theexception of using lithium fluoride having an average particle size of30 nm in place of barium sulfate having an average particle size of 50nm of Example 4. The evaluation results of the obtained separator areshown in Table 2.

Example 25

A separator was fabricated in the same manner as in Example 15 with theexception of using lithium fluoride having an average particle size of30 nm in place of sodium phosphate having an average particle size of500 nm of Example 15. The evaluation results of the obtained separatorare shown in Table 2.

Example 26

A separator was fabricated in the same manner as in Example 1 with theexception of using mixed raw materials obtained by dry-blendingpolyethylene C (14 parts by weight), barium sulfate (86 parts by weight)having an average particle size of 50 nm, and the antioxidant (0.14parts by weight) using a Henschel mixer, in place of the mixed rawmaterials of Example 1. The evaluation results of the obtained separatorare shown in Table 2.

Example 27

A separator was fabricated in the same manner as in Example 1 with theexception of using mixed raw materials obtained by dry-blendingpolyethylene C (10 parts by weight), barium sulfate (90 parts by weight)having an average particle size of 50 nm, and the antioxidant (0.1 partsby weight) using a Henschel mixer, in place of the mixed raw materialsof Example 1. The evaluation results of the obtained separator are shownin Table 2.

Example 28

A separator was fabricated in the same manner as in Example 15 with theexception of using barium sulfate having an average particle size of 50nm in place of sodium phosphate having an average particle size of 500nm of Example 15. The evaluation results of the obtained separator areshown in Table 2.

Example 29

A separator was fabricated in the same manner as in Example 1 with theexception of using mixed raw materials obtained by dry-blendingpolyethylene C (1 part by weight), barium sulfate (99 parts by weight)having an average particle size of 50 nm, and the antioxidant (0.01parts by weight) using a Henschel mixer, in place of the mixed rawmaterials of Example 1. The evaluation results of the obtained separatorare shown in Table 2.

Comparative Example 1

A separator was fabricated in the same manner as in Example 1 with theexception of using mixed raw materials obtained by dry-blendingpolyethylene A (100 parts by weight) and the antioxidant (1 part byweight) using a Henschel mixer, in place of the mixed raw materials ofExample 1. The evaluation results of the obtained separator are shown inTable 1.

Comparative Example 2

Polyethylene B (50 parts by weight), barium sulfate (50 parts by weight)having an average particle size of 660 nm, and the antioxidant (0.5parts by weight) were dry-blended with a Henschel mixer to obtain amixed raw material. Next, the mixed raw material was fed into atwin-screw kneader, and melt-kneaded while heating to 180° C., and theobtained melt-kneaded product was subjected to thermal compression at180° C. to obtain a raw sheet. Thereafter, the raw sheet was subjectedto simultaneous biaxial stretching at a temperature of 135° C. and astretching ratio of 2×2. Subsequently, simultaneous biaxial stretchingat a ratio of 3×3 was carried out at 125° C. The evaluation results ofthe obtained separator are shown in Table 1.

Comparative Example 3

A separator was fabricated in the same manner as in Example 3 with theexception of using silica having an average particle size of 16 nm inplace of barium sulfate having an average particle size of 50 nm ofExample 3. The evaluation results of the obtained separator are shown inTable 1.

Comparative Example 4

A separator was fabricated in the same manner as in Example 3 with theexception of using alumina having an average particle size of 10 nm inplace of barium sulfate having an average particle size of 50 nm ofExample 3. The evaluation results of the obtained separator are shown inTable 1.

Comparative Example 5

A separator was fabricated in the same manner as in Example 3 with theexception of using boehmite having an average particle size of 800 nm inplace of barium sulfate having an average particle size of 50 nm ofExample 3. The evaluation results of the obtained separator are shown inTable 2.

Comparative Example 6

A separator was fabricated in the same manner as in Example 3 with theexception of using potassium titanate (K₂O.8TiO₂) having an averageparticle size of 400 nm in place of barium sulfate having an averageparticle size of 50 nm of Example 3. The evaluation results of theobtained separator are shown in Table 2.

TABLE 1 Examp. Examp. Examp. Examp. Examp. Examp. Examp. Examp. 1 2 3 45 6 7 8 Raw Polyolefin Type PE PE PE PE PE PE PE PE materials resin Useamount 85 70 40 20 85 70 40 20 of (% by weight) separator Mv(10⁴) 70 7070 70 70 70 70 70 Ionic Type BaSO₄ BaSO₄ BaSO₄ BaSO₄ BaSO₄ BaSO₄ BaSO₄BaSO₄ compound Use amount 15 30 60 80 15 30 60 80 (% by weight) Ave.particle 50 50 50 50 10 10 10 10 size (nm) Metal Type — — — — — — — —oxide Use amount — — — — — — — — (% by weight) Ave. particle — — — — — —— — size (nm) Separator Membrane 12 15 18 20 11 14 17 19 propertiesthickness (μm) Porosity (%) 56 60 64 67 53 62 66 70 Air permeability 5065 80 90 45 60 70 80 (sec./100 cc) Puncture 330 400 340 280 320 390 330280 strength (gf) Degree of 103.2 102.1 101.4 100.3 102.8 102.4 100.8100.1 whiteness Voltage resistance 2.2 2.0 1.9 1.8 2.2 2.0 1.9 1.8(kV/20 μm) Solder test (mm²) 8.2 7.8 6.8 5.2 8.0 7.6 6.5 5.0 Test of 20C capacity 39 30 24 22 43 33 28 24 lithium ion retention ratio (%)secondary Capacity retention 80 81 80 80 80 81 80 80 battery ratio after100 cycles(%) Comp. Comp. Comp. Comp. Examp. Examp. Examp. Examp. Examp.Exmp. Examp. 9 10 11 1 2 3 4 Raw Polyolefin Type PE PE PE PE PE PE PEmaterials resin Use amount 20 85 85 100 50 40 40 of (% by weight)separator Mv(10⁴) 70 26 70 70 26 70 70 Ionic Type BaSO₄ BaSO₄ Na₃PO₄ —BaSO₄ — — compound Use amount 80 15 15 — 50 — — (% by weight) Ave.particle 660 50 500 — 660 — — size (nm) Metal Type — — — — — SiO₂ Al₂O₃oxide Use amount — — — — — 60 60 (% by weight) Ave. particle — — — — —16 10 size (nm) Separator Membrane 24 12 14 12 26 17 17 propertiesthickness (μm) Porosity (%) 80 55 55 48 47 65 65 Air permeability 70 5060 130 160 65 65 (sec./100 cc) Puncture 230 240 320 330 340 320 320strength (gf) Degree of 98.2 99.4 101.8 100.3 97.2 95.6 96.5 whitenessVoltage resistance 1.5 2.0 2.1 2.2 1.1 1.3 1.2 (kV/20 μm) Solder test(mm²) 7.0 8.4 8.4 9.4 7.2 6.4 6.2 Test of 20 C capacity 28 39 32 15 9 3030 lithium ion retention ratio (%) secondary Capacity retention 74 80 8074 74 62 68 battery ratio after 100 cycles(%)

TABLE 2 Examp. Examp. Examp. Examp. Examp. Examp. Examp. Examp. Examp.Examp. 12 13 14 15 16 17 18 19 20 21 Raw Polyolefin Type PE PE PE PE PEPE PE PE PE PE materials resin Use amount 70 40 20 5 85 70 40 20 5 85 of(% by weight) separator Mv(10⁴) 70 70 70 200 70 70 70 70 200 70 IonicType Na₃PO₄ Na₃PO₄ Na₃PO₄ Na₃PO₄ Al₂(SO₄)₃ Al₂(SO₄)₃ Al₂(SO₄)₃ Al₂(SO₄)₃Al₂(SO₄)₃ LiF compound Use amount 30 60 80 95 15 30 60 80 95 15 (% byweight) Ave. particle 500 500 500 500 800 800 800 800 800 30 size (nm)Metal Type — — — — — — — — — — oxide Use amount — — — — — — — — — — (%by weight) Ave. particle — — — — — — — — — — size (nm) SeparatorMembrane 18 19 20 22 15 17 19 22 25 13 properties thickness (μm)Porosity (%) 59 64 68 72 58 61 65 70 74 55 Air permeability 70 85 80 10065 75 95 105 100 55 (sec./100 cc) Puncture 300 330 300 260 330 340 310270 240 320 strength (gf) Degree of 101.0 101.9 99.5 99.9 100.7 99.698.6 98.1 98.7 102.0 whiteness Voltage 2.0 1.8 1.8 1.6 1.9 1.8 1.7 1.61.4 2.2 resistance (kV/20 μm) Solder test 7.9 7.2 6.2 5.2 8.3 7.7 7.16.1 5.0 8.3 (mm²) Test of 20 C capacity 32 26 28 20 36 29 21 20 21 38lithium ion retention secondary ratio (%) battery Capacity 81 80 79 7980 81 79 78 79 80 retention ratio after 100 cycles (%) Comp. Comp.Examp. Examp. Examp. Examp Examp. Examp. Examp. Examp. Examp. Examp. 2223 24 25 26 27 28 29 5 6 Raw Polyolefin Type PE PE PE PE PE PE PE PE PEPE materials resin Use amount 70 40 20 5 14 10 5 1 40 40 of (% byweight) separator Mv(10⁴) 70 70 70 200 200 200 200 200 70 70 Ionic TypeLiF LiF LiF LiF BaSO₄ BaSO₄ BaSO₄ BaSO₄ — — compound Use amount 30 60 8095 86 90 95 99 — — (% by weight) Ave. particle 30 30 30 30 50 50 50 50 —— size (nm) Metal Type — — — — — — — — AlOOH K₂O•8TiO₂ oxide Use amount— — — — — — — — 60 60 (% by weight) Ave. particle — — — — — — — — 800400 size (nm) Separator Membrane 15 18 21 23 22 24 25 25 16 19properties thickness (μm) Porosity (%) 59 64 66 71 69 70 72 75 59 56 Airpermeability 65 80 95 100 95 100 110 110 70 85 (sec./100 cc) Puncture390 330 270 250 220 140 80 50 300 310 strength (gf) Degree of 101.4 99.599.6 99.8 100.3 100.2 99.4 99.2 99.0 96.8 whiteness Voltage 2.1 1.9 1.81.6 1.7 1.6 1.6 1.5 1.6 1.7 resistance (kV/20 μm) Solder test 7.7 6.95.3 4.2 4.6 4.2 3.8 2.0 6.7 6.5 (mm²) Test of 20 C capacity 30 25 21 2021 20 18 18 28 23 lithium ion retention secondary ratio (%) batteryCapacity 80 79 81 80 80 79 80 81 66 59 retention ratio after 100 cycles(%)

From Tables 1 and 2, the hole areas in the solder test are smaller andthe heat resistances are superior in Examples 1 to 29, in contrast withthose in Comparative Example 1 in which the ionic compound is notcontained. Furthermore, 20C discharging capacities are significantlyhigher and the capacity retention ratios after 100 cycles are also equalor higher in Examples 1 to 29, as compared with those in ComparativeExample 1. Therefore, it is understood that the separator of the presentembodiment is capable of improving safety, output characteristics, anddurability of the electricity storage device.

Next, in Examples 1 to 29, the 20C discharging capacities are remarkablyhigher and the capacity retention ratios after 100 cycles are equivalentor high as compared with those in Comparative Example 2 in which theseparator was fabricated by the dry pore-forming method without using aplasticizer. Furthermore, Examples 1 to 29 exhibit the higher degrees ofwhiteness of the separator than Comparative Example 2 and are superiorin voltage resistance. Therefore, it is comprehended that the separatorof the present embodiment is superior in improving reliability, outputcharacteristics, and durability of the electricity storage device.

Further, Examples 1 to 29 exhibit the higher degrees of whiteness of theseparator and more favorable voltage resistances as compared withComparative Examples 3, 4 and 6 in which the metal oxides are containedinstead of the ionic compounds. Furthermore, as compared withComparative Examples 3, 4, 5 and 6, Examples 1 to 29 also exhibitremarkably the higher capacity retention ratio values after 100 cycles.Therefore, it is understood that the separator of the present embodimentis superior in terms of improving reliability and durability of theelectricity storage device.

From all those described above, it has clearly been found that theseparator for electricity storage devices which has the porous layercomprising the polyolefin resin and the ionic compound, and exhibits thespecific degree of whiteness, not only favorably functions as aseparator, but also contributes to safety of the electricity storagedevice at elevated temperatures, and furthermore, enables to contributeto the improvement of the output characteristics and durability of theelectricity storage device.

1. A separator for electricity storage devices, which has a porous layercomprising a polyolefin resin and an ionic compound, wherein a contentof the ionic compound in the porous layer is 5% by weight or more andless than 50% by weight in the porous layer and a degree of whiteness ofthe separator is greater than 98.0, and the degree of whiteness ismeasured using a colorimeter under a condition that does not include aspecular reflection light in a 2° viewing angle, and wherein aviscosity-average molecular weight of the polyolefin resin comprised inthe separator for electricity storage devices is 300,000 or more and5,000,000 or less.
 2. The separator for electricity storage devicesaccording to claim 1, wherein the degree of whiteness is 98.5 or moreand 105 or less.
 3. (canceled)
 4. (canceled)
 5. The separator forelectricity storage devices according to claim 1, wherein the polyolefinresin contains polyethylene having a viscosity-average molecular weightof 600,000 or more and 5,000,000 or less.
 6. The separator forelectricity storage devices according to claim 1, wherein a content ofmetal oxide in the separator for electricity storage devices is 10% byweight or less.
 7. The separator for electricity storage devicesaccording to claim 1, wherein the ionic compound has one or more anionsselected from the group consisting of a sulfate ion, a nitrate ion, aphosphate ion, and a halide ion.
 8. The separator for electricitystorage devices according to claim 1, wherein the ionic compound has oneor more cations selected from the group consisting of an alkali metalion and an alkaline earth metal ion.
 9. The separator for electricitystorage devices according to claim 1, wherein the ionic compound isbarium sulfate.
 10. The separator for electricity storage devicesaccording to claim 1, wherein an average particle size of the ioniccompound is 5 nm or more and 600 nm or less.
 11. The separator forelectricity storage devices according to claim 1, wherein an averagepore size of the separator for electricity storage devices is 10 nm ormore and 100 nm or less.
 12. The separator for electricity storagedevices according to claim 1, wherein an air permeability of theseparator for electricity storage devices is 10 seconds/100 ml or longerand 500 seconds/100 ml or shorter.
 13. The separator for electricitystorage devices according to claim 1, wherein a puncture strength of theseparator for electricity storage devices is 100 gf or more and 600 gfor less.
 14. (canceled)
 15. An electricity storage device comprising apositive electrode, a negative electrode, and the separator forelectricity storage devices according to claim
 1. 16. The separator forelectricity storage devices according to claim 1, wherein, when thethickness of the separator is 20 μm or thinner, the degree of whitenessis measured under the condition with the separator that is folded to thetotal thickness of 20 μm or more.